Patent GB-671833-A (GB)
Title: Process for the preparation of surface-active sulphation products and the products thus obtained
IPC: C10G33/04
Filed: 1949-05-04
Abstract: Surface-active compounds are prepared by reacting with a sulphating agent the thick oil obtained as residue from the products of the oxo-synthesis after removal of the monomeric oxo-alcohols and unreacted alkenes, and treating the resultant mixture with an inorganic or organic basic substance to convert the acid-sulphuric esters formed into water soluble neutral salts. The thick oil, which is substantially freed of monomeric oxo-alcohols and unreacted alkenes, as obtained in the synthesis of n+1 oxo-alcohols from alkenes having n-carbon atoms contains branched chain primary dimeric alcohols and branched chain 1 : 3-diols, both having on average 2n+2 carbon atoms, and esters of the monomeric alcohols and 1 : 3-diols; compounds of higher molecular weight may be present.  If desired, the esters in the thick oil may be removed wholly or partially prior to the sulphation, e.g. by subjecting the thick oil or a fraction thereof to catalytic destructive hydrogenation whereby the esters present are converted into branched chain primary dimeric alcohols and monomeric oxo-alcohols, preferably by using as hydrogenation catalyst one containing copper chromite and, in general, temperatures of 200-300 DEG  C. and hydrogen pressures of 200-300 atmos.  Prior to sulphation, the resulting product may be freed, wholly or in part, from the monomeric oxo-alcohols.  If desired, the hydrogenation product may be separated by fractional distillation into one or more relatively narrow fractions and each fraction comprising dimeric alcohols separately sulphated and neutralized.  The thick oil may be prepared from any alkenes, e.g. propene, n-butenes, isobutene, normal or branched pentenes, hexenes, heptenes, octenes, nonenes, decenes and higher alkenes or mixtures thereof or hydrocarbon mixtures consisting predominantly of one or more alkenes; the preferred alkenes have 6-8 carbon atoms.  Sulphation may be carried out with concentrated sulphuric acid, oleum and chlorsulphonic acid, with or without inert diluents or solvents.  Neutralization may be effected, if desired after elimination of excess sulphating agent, with alkali metal hydroxides or carbonates, ammonia and amino compounds.  The surface-active compounds may be extracted from the neutralized mixture with a suitable solvent such as ether.  The products are soluble in water and in hydrocarbons, e.g. gasoline and oil.  They may be used as wetting and dispersing agents (see Group IV (c), as emulsifying agents (see Group III), and some may be used for splitting water-in-oil emulsions.  In examples: (1) 1-hexene is reacted with water gas in an autoclave at elevated temperature and pressure in presence of cobalt-on-kieselguhr catalyst, heated at elevated temperature and hydrogen pressure to decompose dissolved cobalt-carbon monoxide compounds and the oxo-synthesis then completed by hydrogenation using residual catalyst in the reaction mixture, whereupon the product is distilled to remove unreacted hexene and the oxo-alcohols and the residual thick oil is sulphated by means of chlorsulphonic acid in ether and the product is freed from solvent, neutralized with caustic soda and the surface-active material isolated by ethereal extraction; (2) the thick oil of (1) is subjected to destructive hydrogenation using a barium-containing copper chromite-catalyst, the monomeric alcohols formed are distilled from the product and the residue is sulphated and further treated as in (1); (3) the hydrogenation product of (2) is fractionally distilled to recover a fraction of mainly C14-alcohols which is sulphated and further treated as in (1); (4) octene-1 is treated generally as in (1) yielding a thick oil which is also treated as in (1); (5) the thick oil of (4) is subjected to destructive hydrogenation as in (2) and a fraction of largely C18-alcohols is separated by vacuum distillation and sulphated and worked up as in (1); (6) a thick oil is prepared from a C6-8 vapour phase cracking distillate by the method of (1) carried out in continuous fashion, sulphated with 96 per cent H2SO4, the product poured into water, the non-aqueous phase is taken up in 50 per cent aqueous alcohol, neutralized with caustic soda, extracted with pentane to remove non-converted components and the alcoholic solution evaporated to yield the surface-active materials.ALSO:Surface-active agents comprise the water-soluble salts of sulphuric acid esters prepared by sulphating the thick oil obtained in the oxo-synthesis of alcohols after removal of the monomeric oxo-alcohols and unreacted alkenes from the product, or the thick oil or a fraction thereof which has been subjected to catalytic destructive hydrogenation to convert esters present wholly or in part to dimeric alcohols and monomeric oxo-alcohols, or the so treated thick oil from which all or part of the monomeric alcohols have been removed or fractions containing dimeric alcohols, obtained by distillation of the so treated thick oil (see Group IV (b)).  The other principal components of the thick oil are 1 : 3-diols.  The products may be used alone or in conjunction with other substances such as inorganic salts, organic solvents or substances which themselves are surface-active, and they find use as wetting and dispersing agents in the textile, leather and paper industries and as detergents and cleaning agents for textiles and other materials. Reference is made to the alkali metal, ammonia and amine salts of the sulphate esters.ALSO:Emulsifying agents comprise water-soluble salts of sulphuric acid esters prepared by sulphating either the thick oil obtained in the oxo synthesis of alcohols after removal of unreacted alkenes and the monomeric oxo alcohols from the product, or the thick oil or a fraction thereof treated by catalytic destructive hydrogenation to convert esters present wholly or in part to dimeric alcohols and monomeric alcohols, or the so treated oil from which the monomeric alcohols have been removed wholly or in part, or fractions containing dimeric alcohols and obtained by distillation of the so treated thick oil (see Group IV(b)).  The other principal components of the thick oil are 1 : 3 diols.  The preferred compounds are those obtained when higher alkenes, e.g. the C8-9 alkenes have been used in the initial synthesis.  Reference is made to the alkali metal, ammonium and amine salts of the sulphate esters.  In an example: (4), a thick oil derived from an oxo-synthesisi using octene-1 is sulphated and converted into the sodium salt which is dissolved in spindle oil and the solution poured into soft or hard water so forming an emulsion.